DE68922120T2 - Color photographic silver halide materials. - Google Patents

Description

The present invention relates to silver halide color photographic materials, particularly to silver halide color photographic materials for printing, and more particularly to silver halide photographic materials which result in stable color images during long-term storage, sharp color image quality (hereinafter referred to as sharpness), high photographic sensitivity and low photographic fog.

Silver halide color photographic materials are usually spectrally sensitized by adding spectral sensitizers to the silver halides in accordance with the subtractive primary colors. A yellow color-forming coupler, a magenta color-forming coupler and a cyan color-forming coupler are contained in the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer, respectively. After imagewise exposure is carried out, the silver halide color photographic materials are then processed with a color developing solution containing an aromatic primary amine type color developing agent and then treated with a bleach-fixing bath to obtain an image.

However, the resulting color image is not always resistant to light, heat or humidity. In particular, the cyan dye image has greater dark discoloration caused by heat or humidity than either the yellow dye image or the magenta dye image, which changes the color balance. This is a major problem in practical use (for example, the print becomes reddish-brown when kept in an album).

To solve the above problem, JP-A-56-80045 (GB-B-2 066 494, the term "JP-A" as used herein means an "unexamined published Japanese patent application"), JP-A-56-104333 (GB-B 2 068 943), JP-B-57-37857 (US-A-4 333 999) (the term "JP-B" as used herein means an "examined Japanese patent publication"), JP-A-58-105229 (US-A-4 430 423) and JP-A-60-24547 (US-A-4 565 777) teach that couplers present in the 2- and 5-positions of the benzene ring of the Phenols substituted with acylamino groups, i.e. "2, 5-diacylaminophenol" couplers, are particularly excellent as couplers for forming very stable cyan dye images. Phenol cyan couplers having a C2 or higher alkyl group in the 5-position of the phenol can also form very stable cyan dye images.

These phenol cyan couplers are quite useful in the production of color photographic images which are highly heat resistant and have good preservation properties. In addition, photographic materials using these couplers are known to be stable in processing and excellent in color reproduction, particularly due to the preservation of cyan density in bleach-fix processing.

Thus, the phenol couplers mentioned above are favorable compounds for use as cyan dye-forming couplers in color photographic materials.

The standard conditions for selecting cyan couplers include, for example, light resistance, spectral absorption characteristics of the dyes and the effect on photographic properties. Cyan couplers that satisfy these properties are desirable.

On the other hand, image quality is another important property required for color photographic printing materials, which is greatly influenced by sharpness.

In order to improve the sharpness of color images, the following two techniques are usually used. One is to prevent blurring of an image caused by haloing caused by reflection of light scattered on the interface between a silver halide emulsion and a base or on the surface of a photographic material opposite to the silver halide emulsion layers during or after passing through the silver halide emulsion layers and causing reflection of the light into the silver halide emulsion layers, and the other is to prevent blurring of an image caused by radiation caused by scattering of light on the surface of the silver halide in the silver halide emulsion layers.

Silver halide color photographic materials for copies usually use the radiation prevention method.

In order to prevent radiation, the silver halide emulsion layers are dyed. Usually, these layers to be dyed are composed of hydrophilic colloids, and therefore, water-soluble dyes are generally contained in the layers to be dyed. The dyes should satisfy the following conditions.

(1) The dyes must have the correct spectral absorption suitable for the intended use.

(2) The dyes must be photochemically inert, i.e. they must not have any chemical effect on the properties of the photographic silver halide emulsion layers, for example, reducing the sensitivity, fading the latent image or causing photographic fog.

(3) The dyes must be decolourised or dissolved and removed during photographic processing so as not to give rise to undesirable colour on the processed photographic material.

In order to find the dyes satisfying the above conditions, those skilled in the art have been researching diligently and the following dyes have been found, namely, oxonol dyes having pyrazolone or barbituric acid nuclei described in GB-B-506 385, GB-B-1 177 429, GB-B-1 311 884, GB-B-1 338 799, GB-B-1 385 371, GB-B-1 467 214, GB-B-1 433 102 and GB-B-1 553 516, JP-A-48-85103 (GB-B-1 373 026), JP-A-49-114420 (GB-B-1-433 102), JP-A-55-161233, JP-A-59-111640, US-A-3 247 127, US-A-3 469 985 and US-A-4 078 933; the other oxonol dyes described in US-A-2 533 472 and US-A-3 379 533 and GB-B-1 278 621; azo dyes described in GB-B-575 691, GB-B-680 631, GB-B-599 623, GB-B-786 907, GB-B-907 125 and GB-B-1 045 609, US-A-4 255 326 and JP-A-59-211043; Azomethine dyes described in JP-A-50-100116, JP-A-54-118247, GB-B-2 014 598 and GB-B-750 031; anthraquinone dyes described in US-A-2 865 752; Allylidene dyes described in US-A-2 538 009, US-A-2 688 541 and US-A-2 538 008, GB-B-584 609 and GB-B-1 210 252, JP-A-50-40625, JP-A-51-3623, JP-A-51-10927, JP-A-54,118247, JP-B-48-3286 and JP-A-59-37303; styryl dyes described in JP-B-28-3082, JP-B-44-16594 and JP-B-59-28898; Triarylmethane dyes described in GB-B-466 583 and GB-B-1 335 422 and JP-B-59-228250; merocyanine dyes, described in GB-B-1 075 653, GB-B-1 153 341, GB-B-1 284 730, GB-B-1 475 282 and GB-B-1 542 807; and cyanine dyes described in US-A-2 843 486 and US-A-3 294 539.

Of these dyes, the oxonol dyes containing two pyrazolone nuclei have been used for dyeing photographic materials as useful dyes which are decolorized in a developing solution containing sulfite and have little harmful influence on photographic emulsions.

However, many of the oxonol dyes containing two pyrazolone nuclei have the disadvantage that they spectrally sensitize the undesirable regions of the silver halide emulsions or of the spectrally sensitized silver halide emulsions themselves, causing a reduction in sensitivity, probably due to a drop in the spectral sensitizers and increased fog.

In addition, some of them disappear after development processing, which has recently been carried out more quickly. To overcome this problem, it has been proposed to use dyes that have a high reactivity with sulfite ions, but these dyes have disadvantages since they are not sufficiently stable in dry films to cause the reduction in density over time and do not achieve a desired photographic effect.

In addition, combinations of the above dyes and heat-resistant couplers, for example, the above-mentioned 2,5-diacylaminophenol couplers, cause the reduction of sensitivity and the increase of fog. This is a major problem in practical use. JP-A-60-22 5155 discloses that photographic materials prepared by mixing 2,5-diacylaminophenol couplers and specific oxonol dyes have high resistance to dark discoloration, excellent sharpness, good latent image stability and a high degree of whiteness (low fog), but the above combinations have been found to be unsatisfactory with respect to sharpness and fog.

From EP-A-0 186 169 a method for processing silver halide color photographic light-sensitive materials is known which comprises carrying out the processing of a silver halide color photographic light-sensitive material with a stabilizing solution replacing washing with water which comprises a concentration adjustment treatment in the presence of a compound of the general formula given below.

wherein R₆ and R₆' each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R₇ and R₇' each represent a hydroxy group, an alkoxy group, a substituted alkoxy group, a cyano group, a trifluoromethyl group, -COOR₈, -CONHR₈, -NHCOR₈, an amino group, a substituted amino group substituted with an alkyl group having 1 to 4 C atoms or a cyclic amino group represented by the formula

(wherein p and q each represent 1 or 2 and X represents an oxygen atom, a sulfur atom or -CH₂-), R₈ represents a hydrogen atom, an alkyl group or an aryl group, L represents a methine group, n represents 0, 1 or 2, and m and m' each represent 0 or 1.

It is proposed to incorporate into the light-sensitive material a cyan coupler according to one of the formulae (III) to (IV) disclosed in this document for the purpose of storage stability of cyan dyes. Thus, EP-A-0 186 169 proposes an improved system for overcoming the problems encountered in a processing method using a stabilizing solution instead of a water washing method.

EP-A-0 322 702, which constitutes prior art pursuant to Article 54(3) EPC, describes a direct positive photographic material comprising at least one non-prefogged inner silver halide emulsion layer of the latent image type on a support in which a radiation-preventing dye and a cyan coupler are incorporated to prevent a change in photographic performance during preservation and to give images of improved sharpness.

It is the object of the present invention to provide silver halide color photographic materials, including light-sensitive To create silver halide emulsions which give stable colour images, high sharpness, high photographic sensitivity and low photographic fog during long-term storage, by means of new water-soluble dyes which are easily decolourised by processing and are stable during storage without having a deleterious effect on the photographic characteristics of the silver halide emulsion layers.

According to the present invention, this object can be achieved by a silver halide color photographic material comprising a support having at least one silver halide color photographic emulsion layer coated thereon and containing at least one compound represented by the following general formula (I) and at least one compound represented by the following general formula (II) in at least one hydrophilic colloid layer provided on the support:

wherein R₁ and R₂ are each -COOR₅ or

represent

R₃ and R₄ each represent hydrogen or an alkyl group, R�5 and R₆ each represent hydrogen, an alkyl group, a aryl group or R₅ and R₆ together form a 5- or 6-membered ring, Q₁ and Q₂ each represent an aryl group (2- or 3-valent), X₁ and X₂ each represent a 2-valent bonding group or a bond, Y₁ and Y₂ each represent a sulfonic acid group or a carboxylic acid group, L₁, L₂ and L₃ each represent a methine group, m₁ and m₂ each represent 1 or 2, n represents 0, 1 or 2, p₁ and p₂ each represent 0, 1, 2, 3 or 4, and s₁ and s₂ each represent 1 or 2;

wherein Y₃ represents -NHCO- or -CONH-, R₈ represents an aliphatic group, an aromatic group, a heterocyclic group or a substituted or unsubstituted arylamino group, X₃ represents hydrogen, a halogen atom, an alkoxy group or an acylamino group, R₇ represents an alkyl group (having two or more carbon atoms) and Z represents a hydrogen atom or a group which can be released by coupling with an oxidized developing agent, the photographic material not containing a non-prefogged inner silver halide emulsion layer of the latent image type.

In the present invention, the terms "alkyl group (or alkyl component)", "aryl group (or aryl component)" and "aromatic group" include substituted and unsubstituted, respectively.

A detailed explanation of the dyes represented by the formula (I) is given below.

In formula (I), R₁ and R₂ each represent

R₃ and R₄ each represent hydrogen or an alkyl group (e.g. methyl, ethyl), R₅ and R₆ each represents hydrogen, an unsubstituted alkyl group (e.g. methyl, ethyl, isopropyl, butyl), a substituted alkyl group [examples of the substituents include a sulfo group (e.g. sulfomethyl, sulfoethyl), a carboxyl group (e.g. carboxymethyl, carboxethyl), a hydroxy group (e.g. hydroxyethyl, 1,2-dihydroxypropyl), an alkoxy group (e.g. methoxyethyl, ethoxyethyl), a halogen atom [e.g. fluorine, chlorine, bromine (e.g. 2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl)], a cyano group (e.g. cyanoethyl), an aliphatic or aromatic sulfonyl group (e.g. methanesulfonylethyl), a nitro group (e.g. 2-nitrobutyl, 2-nitro-2-methylpropyl), an amino group, unsubstituted or substituted with an alkyl group such as a methyl group and an ethyl group (e.g. dimethylaminoethyl, diethylaminopropyl), an aryl group (e.g. benzyl, p-chlorobenzyl)]; a phenyl group and a substituted phenyl group [examples of the substituents include a sulfo group (e.g. p-sulfophenyl, o,p-disulfophenyl), a carboxyl group (e.g. p-carboxyphenyl, m-carboxyphenyl), a hydroxy group (e.g. p-hydroxyphenyl, m-hydroxyphenyl), an alkoxy group (e.g. p-methoxyphenyl, m-ethoxyphenyl), a halogen atom (e.g. p-chlorophenyl, p-bromophenyl, p-fluorophenyl), a cyano group (e.g. p-cyanophenyl, o-cyanophenyl), a nitro group (e.g. p-nitrophenyl, m-nitrophenyl), an amino group unsubstituted or substituted with an alkyl group such as a methyl group and an ethyl group (e.g. p-dimethylaminophenyl, p-diethylaminophenyl) or an alkyl group (e.g. p-methylphenyl, o-methylphenyl)]. When R₁ and R₂ represent -COOR₅ and R₅ represents hydrogen, R₁ and R₂ represent carboxyl groups which can form not only a free acid but a salt (e.g. a sodium salt, potassium salt, aminonium salt, tetraaminonium salt).

R₅ and R₆ may also form a 5- to 6-membered ring (e.g. morpholino, piperidino). Q₁ and Q₂ each represents a 2- or 3-valent unsubstituted aryl group (e.g., phenyl, naphthyl), a 2- or 3-valent substituted phenyl group [examples of the substituents include a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a halogen atom (chlorine, bromine, fluorine), an aliphatic or aromatic carbamoyl group (e.g., ethylcarbamoyl), an aliphatic or aromatic sulfamoyl group (e.g., ethylsulfamoyl), a cyano group, a nitro group, an alkylsulfonyl group (e.g., methanesulfonyl), an arylsulfonyl group (e.g., benzenesulfonyl), an amino group unsubstituted or substituted with an alkyl group such as a methyl group and an ethyl group (e.g., dimethylamino), an aliphatic or aromatic acylamino group (e.g., acetylamino) and an aliphatic or aromatic sulfonamido group (for example methanesulfonamido)]. Q₁ and Q₂ may be linked to the other components at any position. X₁ and X₂ each represent a 2-valent bonding group and in particular -O-, - -, - -CO-, -SO₂, - -SO₂, or a bond wherein R₇ is hydrogen, a C₁-C₅ alkyl group or a C₁-C₅ (as a whole) substituted alkyl group [examples of the substituents include a C1 -C3 alkoxy group, a sulfo group (e.g. sulfoethyl, sulfopropyl), a carboxyl group (e.g. carboxylethyl), a cyano group, a hydroxy group (e.g. hydroxyethyl), an amino group unsubstituted or substituted with an alkyl group such as a methyl group and an ethyl group, an aliphatic or aromatic sulfonamido group (e.g. methane, sulfonamido), an aliphatic or aromatic carbonamido group (e.g. acetylamino), an aliphatic or aromatic carbamoyl group (e.g. ethylaminocarbonyl) and an aliphatic or aromatic sulfamoyl group (e.g. ethylaminosulfonyl)]. Y1 and Y2 represent a C1 -C3 alkoxy group, a sulfo group (e.g. sulfoethyl, sulfopropyl), a carboxyl group (e.g. carboxylethyl), a cyano group, a hydroxy group (e.g. hydroxyethyl), an amino group unsubstituted or substituted with an alkyl group such as a methyl group and an ethyl group, an aliphatic or aromatic sulfonamido group (e.g. methane, sulfonamido), an aliphatic or aromatic carbonamido group (e.g. acetylamino), an aliphatic or aromatic carbamoyl group (e.g. ethylaminocarbonyl) and an aliphatic or aromatic sulfamoyl group (e.g. ethylaminosulfonyl)]. each represents a sulfonic acid group or a carboxylic acid group which can form not only a free acid but a salt (e.g., sodium salt, potassium salt, ammonium salt, tetraammonium salt). L₁, L₂ and L₃ each represent a methine group or a substituted methine group (in which the substituents include a methyl group, an ethyl group and a phenyl group), m₁ and m₂ each represent 1 or 2, n represents 0, 1 or 2, p₁ and p₂ each represent 0, 1, 2, 3 or 4, s₁ and s₂ each represent 1 or 2.

In the compounds represented by the formula (I), R₃ and R₄ are each preferably hydrogen or a methyl group, R₅ and R₆ are each preferably hydrogen, a C₁-C₄ alkyl group, a C₁-C₆ substituted alkyl group [examples of the substituents preferably include a sulfo group, a carboxyl group, a hydroxy group, a C₁- C₂-alkoxy group, a chlorine atom, a cyano group, an amino group, and a C₁-C₄ alkylamino group], a phenyl group, or a substituted phenyl group [examples of the substituents preferably include a sulfo group, a carboxyl group, a C₁-C₄ alkoxy group, a chlorine atom, a cyano group, a C₁-C₄ alkyl group, an amino group, and a C₁-C₄ alkylamino group]. R₅ and R₆ also preferably form a 5-membered ring or a 6-membered ring (e.g., a morpholino ring, a pyrolidine ring, a piperidine ring). Q₁ and Q₂ each preferably represents a phenyl group, a substituted phenylene group [in which substituents preferably represent a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a halogen atom (e.g. chlorine, bromine, fluorine) and a C₁-C₄ dialkylamino group].

When n, m₁, m₂, P₁, P₂, S₁, and S₂ are each plural, each set of groups may be the same or different.

X₁ and X₂ each preferably represents -O-, - -, or a bond in which R₇ preferably represents hydrogen, a C₁-C₅ alkyl group or a C₁-C₅ substituted alkyl group (examples of the substituents include a C₁-C₃ alkoxy group, a cyano group, a hydroxy group and a C₁-C₄ alkylamino group]. In addition, in the dyes represented by the formula (I), the most preferable dye is obtained when m₁=m₂=1.

Since the dyes of the present invention are preferably those that can easily dissolve in a processing solution to thereby come out of the photographic material, the carbon numbers of an alkyl group and an aryl group are preferably small.

The following are examples of the compounds represented by formula (I).

The compounds of formula (1) can be synthesized by various methods, for example by carrying out a condensation of a pyrazolone represented by formula (III) and a compound represented by formula (IVa), (IVb), (IVc), (IVd) or (IVe), in the presence of bases:

wherein R₁, R₃, Q₁, X₁, Y₁, L₁, L₂, L₃, m₁, n, p₁ and s₁ have the same definition as given above, Z represents hydrogen, a nitro group or a halogen atom (for example, chlorine, bromine), R₈ represents hydrogen, an alkyl group (for example, methyl, ethyl) or a phenyl group and X represents an anion (for example, chloride, bromide, iodide, perchlorate, methyl sulfate, ethyl sulfate, p-toluene sulfate). The other compounds represented by the formula (I) can be synthesized in a similar manner to the process described above.

Examples of bases used in the condensation reaction include pyridine, piperidine, triethylamine, triethanolamine, sodium acetate and potassium acetate.

Examples of solvents used in carrying out the condensation reaction include alcohols (e.g., methanol, ethanol, isopropanol), amides (e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone), nitriles (e.g., acetonitrile), dimethyl sulfoxide, ethylene glycol, ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol diethyl ether), water, and a mixture of water and the solvents described above. The amount of the solvent in the mixture is preferably 1 to 1000 parts by volume per part by volume of water.

The reaction temperature can be selected from the range of 0ºC to the boiling point of the solvent.

The reaction time is determined depending on the reaction temperature and is generally selected in the range of about 30 minutes to about 3 days.

A pyrazolone represented by formula (III) is used in the condensation reaction in an amount of 0.1 to 3 moles per mole of a compound represented by formula (IVa), (IVb), (IVc), (IVd) or (IVe).

The synthesis examples of the compounds represented by the formula (I) are described below.

Synthesis example I (compound 3)

To 50 ml of ethanol was added 5.2 g of 3-ethoxycarbonyl-1-(2-sulfobenzyl)-pyrazolin-5-one, and then 4.2 ml of triethylamine and 1.5 g of malondialdehyde dianilate. The mixture was heated and refluxed for three hours to obtain a uniform solution. To this hot solution was added a solution prepared by dissolving 1.2 g of sodium acetate in 15 ml of methanol with stirring. Then 25 ml of isopropanol was added to the above solution to precipitate a dark purple crystal. This crystal was filtered out, washed with isopropanol and dried to give 2 g of compound 3.

Melting point higher than 300ºC

λH₂O: 551 nm ε: 6.73x10�sup4;

max (ε: extinction exponent)

Synthesis example 2 (compound 8)

A mixture consisting of 7.4 g of 3-carboxy-1-(2-sulfobenzyl)-pyrazolin-5-one, 50 ml of methanol and 7.5 ml of triethylamine was prepared and cooled with ice. To this mixture was added 2.8 g of glutaraldehyde dianil hydrochloride with stirring for three hours. To this solution was added a solution prepared by dissolving 4.2 g of sodium acetate in 50 ml of methanol and another 25 ml of isopropanol to to precipitate a dark purple crystal. This crystal was filtered, washed with isopropanol, and dried to give 5.4 g of compound 8.

Melting point: higher than 300ºC

λH₂O : 626 nm ε: 7.89x10�sup4;

Max

Synthesis example 3 (compound 10)

A mixture consisting of 8 g of 3-(2-hydroxyethylcarbamoyl)-1-(2- sulfobenzyl)-pyrazoline, 30 mL of methanol and 3.8 mL of triethylamine was prepared and cooled. To this solution were added 3 g of glutaraldehyde dianilate and then 2 mL of acetic anhydride. The mixture was reacted at room temperature for 1 hour and then 20 mL of isopropanol was added to precipitate a black crystal. The black crystal was filtered out, washed with isopropanol and dried to give 6.1 g of compound 10.

Melting point higher than 300ºC

λH₂O: 633 nm ε:8.8x10�sup4;

Max

Synthesis example 4 (compound 18)

A mixture consisting of 8 g of 3-carboxy-1-[2-(4-sulfophenyl)ethyl]-pyrazolin-5-one, 50 ml of methanol and 7 ml of triethylamine was prepared, and then 1.6 g of N,N-diphenylformamidine hydrochloride was added and heated for 2 hours to prepare a uniform solution. To this solution was added a solution prepared by dissolving 4.5 g of sodium acetate in 50 ml of methanol and another 20 ml of isopropanol to precipitate a yellow crystal. This crystal was filtered out, washed with isopropanol washed and dried to give 4 g of compound 18.

Melting point: higher than 300ºC

λH₂O: 452 nm ε:2.10x10�sup4;

Max

Synthesis example 5 (compound 12)

Compound 12 was obtained using 3-ethoxycarbonyl-1-(2,4-disulfobenzyl)-pyrazolin-5-one in the same manner as Synthesis Example 2.

Melting point: higher than 300ºC

λH₂O: 640 nm ε:7.02x10�sup4;

Max

Synthesis example 6 (compound 20)

Compound 20 was obtained using 3-carboxy-1-[2- (4-sulfobutyloxy)-benzyl]-pyrazolin-5-one in the same manner as in Synthesis Example 2.

Melting point: 264 to 269ºC (decomposition)

λH₂O: 628 nm ε: 7.39x10�sup4;

Max

The compounds represented by formula (II) are non-diffusible cyan couplers.

The compounds according to formula (II) are described in detail below.

In formula (II), R₈ represents a chain or cyclic-aliphatic group preferably having 1 to 31 (total) C atoms (for example methyl, butyl, pentadecyl, cyclohexyl), an aromatic group, preferably with 6 to 32 (in total) C atoms (for example phenyl, naphthyl), a heterocyclic group, preferably a 5- to 7-membered ring containing at least N, O and/or S atoms as heteroatoms (for example 2-pyridyl, 3-pyridyl, 2-furanyl, 2-oxazolyl) or a substituted amino group, preferably substituted with at least one alkyl and/or aryl group. These groups can be substituted by a substituent selected from an alkyl group, an aryl group, an alkoxy or aryloxy group (for example methoxy, dodecyloxy, methoxyethoxy, phenyloxy, 2,4-di-tert.-amylphenoxy, 3-tert.-butyl-4-hydroxyphenyloxy, naphthyloxy), a carboxyl group, an alkylcarbonyl or arylcarbonyl group (for example acetyl, tetradecanoyl, benzoyl), an alkoxycarbonyl or aryloxycarbonyl group (for example methoxycarbonyl, benzyloxycarbonyl, phenoxycarbonyl), an aliphatic or aromatic acyloxy group (for example acetyl, benzoyloxy, phenylcarbonyloxy), an aliphatic or aromatic sulfamoyl group (for example N-ethylsulfamoyl, N-octadecylsulfamoyl), an aliphatic or aromatic carbamoyl group (for example N-ethylcarbamoyl, N-methyldodecylcarbamoyl), an aliphatic or aromatic sulfonamido group (for example methanesulfonamido, benzenesulfonamido), an aliphatic or aromatic acylamino group (for example acetylamino, benzamido, ethoxycarbonylamino, phenylaminocarbonylamino), an imido group (e.g. succinimido, hydantomyl), an aliphatic or aromatic sulfonyl group (e.g. methanesulfonyl), a hydroxy group, a cyano group, a nitro group and a halogen atom.

In describing the present invention, the term "an aliphatic group" means a straight-chain, a branched chain or cyclic aliphatic hydrocarbon group which may be a saturated or unsaturated group, such as an alkyl, alkenyl or alkynyl group.

In formula (II), R₇ represents a C₂-C₂₀ (total) alkyl group (e.g. ethyl, butyl, pentadecyl). In formula (II), X₃ represents hydrogen, a halogen atom (e.g. Cl, Br, F), an aliphatic group (e.g. methyl, propyl, allyl), an alkoxy group (e.g. methoxy, butoxy) or an aliphatic or aromatic acylamino group (e.g. acetoamide).

In formula (II), Z represents hydrogen or a coupling-releasing group such as a halogen atom (e.g. fluorine, chlorine, bromine), an alkoxy group (e.g. ethoxy, dodecyloxy, methoxycarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy), an aryloxy group (e.g. 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), an aliphatic or aromatic acyloxy group (e.g. acetoxy, tetradecanoyloxy, benzoyloxy), an aliphatic or aromatic sulfonyloxy group (e.g. methanesulfonyloxy, toluenesulfonyloxy), an amido group (e.g. dichloroacetylamino, heptabutyrylamino, methanesulfonylamino, toluenesulfonylamino), an alkoxycarbonyloxy group (e.g. ethoxycarbonyloxy, benzyloxycarbonyloxy), an aryloxycarbonyloxy group (e.g. Phenoxycarbonyloxy), an aliphatic or aromatic thio group (e.g. ethylthio, phenylthio), a heterocyclic ring thio group (e.g. tetrazolylthio), an imido group (e.g. succinimido, hydantoinyl), and a heterocyclic ring containing at least one N atom (e.g. 1-pyrazolyl, 1-benzotriazolyl), an aromatic azo group (e.g. phenylazo). These releasing groups can contain photographically useful groups.

In formula (II), R₇ is preferably a C₂-C₁₅ alkyl group, more preferably a C₂-C₄ alkyl group.

In the formula (II), Z is preferably hydrogen or a halogen atom, more preferably a halogen atom. In the formula (II), X₃ is preferably a halogen atom.

The compounds represented by formula (II) and their synthesis method are disclosed, for example, in US-A-4,564,590, US-A-2,895,826, US-A-4,557,999, US-A-4,565,777, US-A-4,124,396, US-A-4,613,564, US-A-4,327,173, US-A-4,564,586 and US-A-4,430,423, JP-A-61-39045, JP-A-62-70846, JP-A-61-390441 and JP-A-62-257158.

The following are examples of compounds represented by the formula (II) of the present invention.

The dyes of formula (1) can be used as filter dyes, radiation-preventing dyes or antihalation dyes in any effective amount, preferably in an amount such that the dye provides an optical density (of the total hydrophilic colloid layers) of 0.05 to 3.0. Their addition is carried out during any step of processing prior to the application of a photographic coating composition to a support.

In order to eliminate spectral absorption which is harmful to spectral sensitizers, it is preferable to use a dye represented by formula (I) where n=1 for a green-sensitive dye and a dye represented by formula (I) where n=2 for a red-sensitive dye.

The dyes of the present invention can be dispersed in at least one of the hydrophilic colloid layers, i.e. emulsion layers, and the other hydrophilic colloid layers (intermediate layer, protective layer, antihalation layer, including backing layer and filter layers) by various known methods.

(1) A method of dissolving or dispersing the dyes of the present invention directly in coating compositions of emulsion layers and hydrophilic colloid layers, or a method of dissolving or dispersing the dyes of the present invention in an aqueous solution or solvent and then using the resulting solution or dispersion in emulsion layers and hydrophilic colloid layers. The dyes of the present invention can be dissolved in a suitable solvent, for example, methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve, halogenated Alcohol (described in JP-A-48-9715 and US-A-3,756,830), acetone, water, pyridine or mixtures thereof, and the resulting solution can be added to emulsions or a hydrophilic colloid solution.

(2) A method of introducing a hydrophilic copolymer having the electric charge opposite to the dye ion in the layers as an etchant and localizing the dyes in the specific layers by interaction between the polymer and the dye molecules. The term "polymeric etchants" means polymers containing secondary and tertiary amino groups, polymers having a nitrogen-containing heterocyclic region, and polymers containing these quaternary cationic groups having a molecular weight of 5,000 or more, most preferably 10,000 or more.

Suitable etchants include, for example, vinylpyridine polymers and vinylpyridinium cation polymer described in US-A-2 548 564, vinylimidazolium cation polymer described in US-A-4 124 386, polymer etchants capable of crosslinking with gelatin disclosed in US-A-3 625 694, aqueous sol-like etchants disclosed in US-A-3 958 995 and JP-A-54-115228, water-insoluble etchants disclosed in US-A-3 898 088, reactive etchants capable of being covalently bonded to the dyes disclosed in US-A-4 168 976, polymers derived from an ethylenically unsaturated compound having a dialkylaminoalkyl ester residue as in GB-B-685 475, products resulting from the reaction of polyvinyl alkyl ketone and aminoguanidine as described in GB-B- 850 281 and polymers derived from 2-methyl-1-vinylimidazole as described in US-A-3 445 231.

(3) A method of dissolving the compound using surfactants. The surfactants may be oligomers or polymers.

A detailed description of the oligomers and polymers described above is given in the specification of JP-A-60-158437, pages 19 to 27. The hydrazole of a lipophilic polymer as described in JP-B-51-39835 can be added to the hydrophilic colloid dispersion obtained above.

The cyan coupler represented by formula (II) may be used in an amount of 0.1 to 1 mol, preferably 0.2 to 0.5 mol, per mol of silver halide in the photographic silver halide layer containing the cyan coupler.

The cyan couplers represented by formula (II) are dissolved in high-boiling organic solvents (e.g., phthalic acid ester solvents, phosphate solvents, fatty acid ester solvents), and the resulting solutions are dispersed in hydrophilic colloid media to be added to the silver halide emulsions.

In order to improve the storage properties of silver halide color photographic materials, benzotriazole ultraviolet absorbers and substantially water-insoluble organic solvent-soluble polymers may be added. In particular, the use of these polymers is effective for improving dark discoloration. As the most useful polymers, those described in JP-A-71262 are mentioned.

The hydrophilic colloids typically include gelatin and also any other conventionally known colloids used for photographic materials.

In the present invention, silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride can be used as the silver halide. For the purpose of rapid processing, in particular, silver chlorobromide containing 90 mol% or more of silver chloride (preferably 98 mol%) is favorable.

This silver chlorobromide may contain some silver iodide, but preferably does not contain any silver iodide.

The grains of silver halide according to the present invention may be in the form of regular crystals such as a cube or an octahedron, or irregular crystals such as a sphere or a table, or combinations thereof. A mixture of grains having different crystal shapes may also be used, but those in the form of regular crystals are particularly preferred.

The silver halide grains of the present invention may consist of different phases or a uniform phase as regards the inner layer and the surface layer. The grains may also be those which form latent images mainly on the surface thereof (e.g., negative emulsion) or mainly on the inner side (e.g., inner latent image emulsion, prefogged direct reversal emulsion). Preferably, the grains are those which can form latent images mainly on the surface.

The silver halide emulsions to be used in the present invention are preferably tabular grain emulsions in which the grains have a thickness of 0.5 µm or less, preferably 0.3 µm or less, a diameter of preferably 0.6 µm or more and an average height-to-width ratio of 5 or more, occupy 50% or more of the entire above range, or monodisperse emulsions such that the statistical coefficient of variation (a value of s/ obtained by dividing the standard deviation s by a diameter in the distribution represented by a diameter of a circle in the vicinity of the above ranges) is 20% or less. Two or more tabular grain emulsions and monodisperse emulsions may also be mixed.

The photographic emulsions to be used in the present invention can be prepared by the methods described in P. Glafkides, "Chimie et Physique Photographique" (Paul Montel Co., Ltd., 1967), G.F. Duffin, "Photographic Emulsion Chemistry" (Focal Press, 1966), and V.L. Zelikman, "Making and Coating Photographic Emulsion" (Focal Press, 1964).

In order to control the growth of the grains, silver halide solvents such as ammonia, potassium thiocyanate, ammonium thiocyanate, thioether compounds (e.g. US-A-3,271,157, US-A-3,574,628, US-A-3,704,130, US-A-4,297,439, US-A-4,276,374), thione compounds (e.g. JP-A-53-144319, JP-A-53-82408, JP-A-55-77737), and amine compounds (e.g. JP-A-54-100717) can be used in the formation of silver halide grains.

In the process for producing or physically ripening silver halide grains, a cadmium salt, a Zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, or an iron(III) salt or an iron(III) complex salt thereof may be used.

Silver halide emulsions are usually chemically sensitized, for example by the methods described in "The Fundamentals of Photographic Processes with Silver Halides" edited by H. Frieser, (Akademische Verlagsgesellschaft, 1968) pages 675 to 734.

There may be used a sulfur sensitization method using sulfur-containing compounds capable of reacting with active gelatin or silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines), a reduction sensitization method using reducible materials (e.g., stannous salt, amines, hydrazine derivatives, formamidine sulfinic acid, silane compound), and a noble metal sensitization method using noble metal compounds (e.g., gold complexes and other complexes of metals belonging to Group VIII of the Periodic Table such as Pt, Ir and Pd) alone or in combination.

In order to avoid photographic fog in the production step, preservation or processing of the photographic materials or to stabilize the photographic properties, the photographic silver halide emulsions to be used according to the invention can contain various compounds, for example azoles such as benzothiozolium salt, nitroindazoles, triazoles, benzotriazoles and benzimidazoles (especially those with nitro or halogen substituents, heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, Mercaptothiadioazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), and mercaptopyrimidines; these heterocyclic mercapto compounds have water-soluble groups such as a carboxyl group and a sulfone group, thioketo compounds such as oxazolinethione, azaindenes such as tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a,7)-tetraazaindenes), benzenethiosulfonic acids and benzenesulfinic acids as antifoggants or stabilizers.

The silver halide photographic emulsions of the present invention may contain color couplers such as a cyan coupler, a magenta coupler, a yellow coupler and compounds for dispersing couplers.

The photographic silver halide emulsions according to the invention can contain compounds which form color by oxidation coupling with an aromatic primary amine developing agent (for example phenylenediamine derivatives, aminophenol derivatives) during color development. For example, there are 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, pyrazolotriazole couplers and open-chain acylacetonitrile couplers as magenta couplers and acylacetoamide couplers (for example benzoylacetanilides, pivaloylacetanilides) as yellow couplers.

These couplers are preferably non-diffusible couplers with hydrophobic groups in the molecule, called ballast groups. The couplers can be 4-equivalent or 2-equivalent to a silver ion, or colored couplers with the effect of color correction or couplers that release development retarders during development (the so-called DIR couplers).

The couplers other than DIR couplers may contain colorless DIR coupling compounds which form colorless coupling reaction products and release development retarders. Ultraviolet absorbers and discoloration inhibitors may also be added, such as cinnamic acid esters and 2(2-hydroxyphenyl)benzotriazole.

These discoloration inhibitors include compounds described in the following patents: US-A-3,432,300, US-A-3,573,045, US-A-3,574,627, US-A-3,700,455, US-A-3,764,337, US-A-3,935,016, US-A-4,254,216, US-A-4,268,593, US-A-4,430,425, US-A-4,465,757, US-A-4,465,765, US-A-4,518,679, GB-B-1,347,556, GB-A-2,066,975, JP-A-52-152225, JP-A-53-17729, JP-A-53-20327, JP-A-54-145530, JP-A-55-6321, JP-A-55-21004, JP-A-61-72246, JP-A-61-73152, JP-A-61-90155, JP-A-61-90156 and JP-A-61-145554.

The photographic emulsions according to the invention can contain, for example, polyalkylene oxide or derivatives thereof, such as ethers, esters and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives and 3-pyrazolidones in order to increase the sensitivity and contrast or to accelerate the development.

In the silver halide photographic emulsions of the present invention, known water-soluble dyes (e.g., oxonol dye, hemioxonol dye and merocyanine dye) can be used as filter dyes or radiation-preventing dyes in addition to the dyes disclosed in the present invention. Other known cyanine dyes, merocyanine dyes and hemicyanine dyes other than those disclosed in the present invention The dyes disclosed can also be used as spectral sensitizers.

The photographic emulsions of the present invention may contain various surface active agents for use as coating aids and antistatic agents, agents for imparting improved slip properties, emulsion dispersants, anti-adhesion agents and agents for improving photographic properties (e.g., accelerating development, providing high contrast, sensitizing). The photographic materials of the present invention may also contain various additives such as discoloration preventing agents, hardening agents, color antifogging agents, ultraviolet absorbers and protective colloids such as gelatin, which are particularly described in Research Disclosure, Vol. 176 (1978, XII) RD-17643.

The finished emulsions are applied to a suitable support, such as baryta paper, resin-coated paper, synthetic paper, triacetate film, polyethylene terephthalate film or other plastic supports or glass plates

The silver halide photographic materials of the present invention include a color positive film, color paper, a color negative film, a color reversal film (which may or may not contain couplers), photographic materials for plate making processes (e.g., offset printing film, offset printing duplicate film), photosensitive materials for cathode ray tube display (e.g., photosensitive materials for emulsion X-ray recording, direct or indirect photographic materials using a screen), photographic materials for a silver salt diffusion transfer process, photographic materials for a dye diffusion transfer process, photographic materials for a dye transfer process, an inhibition transfer process, photographic materials for a silver dye bleach process, photographic materials for recording on daylight paper, photographic materials for direct copying of images, photographic materials for development under heat and photographic materials for physical development.

The exposure to form photographic images can be carried out using various well-known light sources, such as natural light (sunlight) or a tungsten lamp, a fluorescent lamp, a mercury vapor lamp, a xenon arc lamp, a carbon arc lamp, a xenox flashlight and a cathode ray tube light spot. The exposure time is usually in a range of 1/1000 to 30 seconds, but may be shorter than 1/1000 seconds, for example in a range of 1/104 to 1/106 seconds when a xenon flashlight or a cathode ray tube is used, or longer than 30 seconds. The spectral composition of the light to be used for the exposure can be controlled with color filters if desired. Laser beams can be used for the exposure. In addition, exposure can be carried out using light from a phosphor excited by an X-ray, Y-ray or α-ray.

The photographic processing of the photographic materials of the present invention can be carried out by known methods and processing solutions as described, for example, in Research Disclosure No. 176, pages 28 to 30 (RD-17643). This photographic processing can be carried out to form silver images (black and white photographic processing) or color images (color photographic processing). The processing temperature is usually in a range of 18 to 50ºC, but may be lower than 18ºC or higher than 50ºC.

The present invention has no limitation with respect to the methods of processing color photographic images. Typically, conventional methods include a method of performing exposure, color development, bleach-fixing and, if necessary, washing and stabilizing, a method of performing exposure, color development, bleaching, fixing and, if necessary, washing and stabilizing, and a method of performing exposure, development with a developing solution containing a black-and-white developing agent, uniform exposure, color development, bleach-fixing and, if necessary, washing and stabilizing, and a method of performing exposure, development with a developing solution containing a black-and-white developing agent, further development with a color developing solution containing a fogging agent (e.g., sodium borohydride), bleach-fixing and, if necessary, washing and stabilizing.

The aromatic primary amine color developing agents to be used in the color developing solutions of the present invention include those which are known and generally used in various color photographic processes, for example, aminophenol and p-phenylenediamine derivatives. Preferably, p-phenylenediamine derivatives are used, and typical examples thereof are given below.

D-1 N,N-Diethyl-p-phenylenediamine

D-2 2-Amino-5-diethylaminotoluene

D-3 2-Amino-5-(N-ethyl-N-laurylamino)-toluene

D-4 4-[N-Ethyl-N-(β-hydroxyethyl)-amino]-aniline

D-5 2-methyl-4-[N-ethyl-N-(β-hydroxyethyl)-amino]- aniline

D-6 N-Ethyl-N-(β-methanesulfonamideethyl)-3-methyl-4- aminoaniline

D-7 N-(2-Amino-5-diethylaminophenylethyl)-methanesulfonamide

D-8 N,N-Dimethyl-p-phenylenediamine

D-9 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline

D-10 4-Amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline

D-11 4-Amino-3-methyl-N-ethyl-N-β-butoxyethylaniline

These p-phenylenediamine derivatives may be in the form of salts such as a sulfate, hydrochloride, sulfite and p-toluenesulfonate. The above-mentioned compounds are described in US-A-2,193,015, US-A-2,552,241, US-A-2,566,271, US-A-2,592,364, US-A-3,656,950 and US-A-3,698,525. These aromatic primary amine color developing agents are used in an amount of about 0.1 g to about 20 g, preferably about 0.5 g to about 10 g per 1 liter of a developing solution.

The color developer solutions to be used according to the invention may contain hydroxylamines, as is well known.

Hydroxylamines can be used in the form of free amines in the color developing solutions, but they are generally in the form of aqueous solutions of the acid salts such as sulfate, oxalate, chloride, phosphate, carbonate and acetate thereof. Hydroxylamines can be substituted or unsubstituted. The nitrogen atoms of the hydroxylamines can be substituted with alkyl groups.

Hydroxylamines are added in an amount of preferably 0 to 10 g, more preferably 0 to 5 g, per 1 liter of a color developing solution. As for the stability of a color developing solution, the smaller amount is better. As for preservatives, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite and potassium metasulfite and carbonyl sulfite additives may be added in an amount of preferably 0 g to 20 g per 1 liter, more preferably 0 g to 5 g per 1 liter. As for the stability of a color developing solution, the smaller amount is better.

As other preservatives, aromatic polyhydroxy compounds described in JP-A-52-49828, JP-A-56-47038, JP-A-56-32140, JP-A-59-160142 and US-A-3 746 544, hydroxyacetones described in US-A-3 615 503 GB-B-1 306 176, α-aminocarbonyl compounds described in JP-A-52-143020 and JP-A-53-89425, various metals described in JP-A-57-44148 and JP-A-57-53749, various saccharides described in JP-A-52-102727, hydroxamic acids described in JP-A-52-27638, α,α-dicarbonyl compounds described in JP-A-59-160141, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, poly(alkyleneimines) described in JP-A-56-94349 and gluconic acid derivatives described in JP-A-56-75647. Hydrazine-N,N-diacetic acid is also preferred. These preservatives can be used in a combination of two or more if desired. In particular, 4,5-dihydroxy-m-benzenedisulfonic acid, poly(ethyleneimine) and triethanolamine are preferably added.

The colour developing solutions to be used according to the invention have a pH value of preferably 9 to 12, more preferably from 9 to 11, and may contain other compounds known as components of developing solutions.

The detailed description of the types and amounts of preservatives, buffers, chelating agents, development accelerators, antifoggants and brightening agents is given in JP-A-63-229457, pages 11 to 19.

In the present invention, the color developing solution is preferably used at a processing temperature in the range of 20 to 50°C, preferably 30 to 40°C, at a processing time of 20 seconds to 5 minutes, preferably 30 seconds to 4 minutes, and is replenished in an amount of 30 to 1000 ml, preferably 60 to 400 ml, per 1 m² of the photographic material, although the smaller amount is better. The desilvering process of the present invention is usually carried out as follows. The desilvering process may generally comprise either a bleaching step/fixing step, a fixing step/bleach-fixing step, a bleaching step/bleach-fixing step and a bleach-fixing step. The desilvering step is carried out for 2 minutes or less, more preferably for 15 to 90 seconds.

In the present invention, bleaching solutions, bleach-fixing solutions, fixing solutions and additives added to the solutions in the amounts described in, for example, JP-A-63-229457, pages 20 to 25, can be used.

Washing and/or stabilization after desilvering can be carried out in the same manner as described in JP-A-63-229457, pages 25 to 29, line 12.

The present invention is illustrated in more detail by the following specific examples. All parts, percentages and ratios are by weight unless otherwise indicated.

example 1

The sample (1) for a multilayer color copy with the following layer structure was prepared on a paper support laminated with polyethylene on both sides.

Layer structure

The composition of each layer is shown below. Numbers indicate the amounts of coatings (g/m²), and the amounts of silver halide emulsions are calculated as silver. However, the amounts of cyan couplers and dyes are given in mol/m².

carrier

Polyethylene laminated paper in which the polyethylene on the first layer side contained a white pigment (TiO2) and a blue dye (ultramarine).

The first layer (blue-sensitive silver halide emulsion layer

Monodisperse silver chlorobromide emulsion containing a spectral sensitizer (Sen-1) (EM-1) 0.16

Monodisperse silver chlorobromide emulsion containing a spectral sensitizer (Sen-1) (EM-2). 0.10

Antifoggant (Cpd-1) 0.004

Gelatin 1.83

Yellow coupler (ExY) 0.83

Color Image Stabilizer (Cpd-2) 0.03

Polymers (Cpd-3) 0.08

Solvent (Solv-1 and Solv-2 in a volume ratio of 1:1) 0.35

Hardener (Hd) 0.02

The second layer (color mixing prevention layer)

Gelatine 1.25

Color mixing preventive agent (Cpd-4) 0.04

Solvent (Solv-3 and Solv-4 in a volume ratio of 1:1) 0.20

Hardener (Hd) 0.02

The third layer (green-sensitive silver halide emulsion layer

Monodisperse silver chlorobromide emulsion containing spectral sensitizers (Sen-2,3) (EM-3) 0.05

Monodisperse silver chlorobromide emulsion containing spectral sensitizers (Sen-2, 3) (EM-4). 0.11

Antifoggant (Cpd-5) 0.001

Gelatin 1.79

Magenta coupler (ExM) 0.32

Color Image Stabilizer (Cpd-6) 0.20

Color Image Stabilizer (Cpd-7) 0.03

Color Image Stabilizer (Cpd-8) 0.03

Solvents (Solv-3 and Solv-5 in a 0.65

Volume ratio of 1:2)

Hardener (Hd) =,01

The fourth layer (ultraviolet absorption layer)

Gelatin 1.58

Ultraviolet absorbers (UV-1/2/3 in a 0.62

Molar ratio of 1:4:4)

Color mixing preventive agent (Cpd-4) 0.05

Solvent (Solv-6) 0.34

Dye (Dy-1) 1.8x1 0.05 (mol/m²)

Dye (Dy-2) 2.0x10⊃min;⊃5;(mol/m²)

Hardener (Hd) 0.01

The fifth layer (red-sensitive silver halide emulsion layer

Monodisperse silver chlorobromide emulsion (EM-5) containing spectral sensitizer (Sen-4,5) 0.07

Monodisperse silver chlorobromide emulsion (EM-6) containing spectral sensitizers (Sen-4, 5). 0.15

Antifoggant (Cpd-9) 0.0002

Gelatin 1.34

Cyan coupler in Table 2 6.7x10⊃min;⊃4; (mol/m²)

Ultraviolet absorbents (UV-1/3/4 in a molar ratio of 1:3:3)0.17

Polymers (Cpd-3) 0.33

Solvent (Solv-l) 0.23

Hardener (Hd) 0.01

The sixth layer (ultraviolet absorption layer)

Gelatin 0.53

Ultraviolet absorbers (UV-1/2/3 in a 0.21

Molar ratio of 1:4:4)

Solvent (Solv-6) 0.08

Hardener (Hd) 0.01

The seventh layer (protective layer)

Gelatin 1.33

Acrylic denatured copolymer of polyvinyl alcohol (denaturation level 17%) 0.17

Liquid paraffin 0.03

The silver halide emulsion (EM-1) used in the above sample was prepared as follows:

(Solution 1)

H2O 1000 ml

NaCl 5.5g

Gelatine 25g

(Solution 2)

Sulfuric acid (IN) 20 ml

(Solution 3)

A compound of the following formula 2 ml (1% aqueous solution)

(Solution 4)

KBr 2.80 g

NaCl 0.34g

H₂O added to 140 ml

(Solution 5)

AgNO3 5g

H₂O added to 140 ml

(Solution 6)

KBr 67.2 g

NaCl 8.26 g

K₂IrCl₆ (0.001% aqueous solution) 0.7 ml

H₂O added to 320 ml

(Solution 7)

AgNO3 120g

NH₄NO₃ (50% aqueous solution) 2 ml

H₂O added to 320 ml

Solution 1 was heated to 74°C, to which solutions 2 and 3 were added. Then, solutions 4 and 5 were added simultaneously in 9 minutes. After another 10 minutes, solutions 6 and 7 were added simultaneously in 45 minutes. Then, the mixed solution was allowed to stand for 5 minutes after addition and then cooled and desalted. Water and dispersion gelatin were added to adjust the pH to 6.2 to obtain a monodisperse cubic silver chlorobromide emulsion having an average particle size of 0.96 µm, a coefficient of variation (a value obtained by dividing the standard deviation by an average particle size s/ ) of 0.08 and 80 mol% of silver chlorobromide. This emulsion was optimally chemically sensitized with sodium thiosulfate.

The other silver chlorobromide emulsions (EM-2) to (EM-6) were prepared in a manner similar to the above emulsion (EM-1) except that the amounts of chemicals, temperature and time were changed.

Table 1 below shows the details of these emulsions Table 1 Emulsion name Form Average particle size Br content (mol%) Coefficient of variation Cube

Coefficient of variation = standard deviation/average particle size

Samples (2) to (7) were prepared in the same manner as the above sample (1) except that the dyes of the fourth layer and the cyan coupler of the fifth layer were changed. The compositions of the dyes and cyan couplers are shown in Table 2. Note that the numbers of the dyes and cyan couplers are the same as those shown in the examples. The cyan coupler (C) below was used for comparison purposes. Cyan coupler (C) Table 2 Sample Dye (Amount used) Cyan coupler (6.7x10⊃min;⊃4; mol/m2) Control Present invention (molar ratio 1:1)

Samples (1) to (7) were subjected to gradation exposure for the purpose of sensitivity measurement through a red filter using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 320ºK). In this regard, exposure was carried out for 0.1 second to obtain an exposure of 250 CMS. As for sharpness, exposure was carried out through an optical wedge for the purpose of sharpness to obtain a cyan density of 1.5.

After exposure, the subsequent steps of color development, bleach-fixation and washing were carried out. Processing step Temperature (ºC) Time Colour development Bleach-fixing Washing Drying

The composition of each processing solution was as follows

Color developing solution

Water 800 ml

Diethylenetriaminepentaacetic acid 1.0 g

Nitrilotriacetic acid 1.5 g

Benzyl alcohol 15 ml

Diethylene glycol 10 ml

Sodium sulphite 2.0 g

Potassium bromide 0.5 g

Potassium carbonate 30 g

N-Ethyl-N-(ß-methanesulfonamideethyl)- 3-methyl-4-aminoaniline sulfate 510 g

Hydroxylamine sulfate 4.0 g

Whitening agent (WHITEX 4B, manufactured by Sumitomo Chemical Co., Ltd.) Water Balance per 1000 ml 1.0 g

pH (25ºC) 10.20

Bleach-fixing bath

Water 400ml

Ammonium thiosulfate (70% aqueous solution) 150 ml

Sodium sulphite 18 g

Iron(III) ammonium ethylenediaminetetraacetate 55 g

Disodium ethylenediaminetetraacetate Water balance to 1000 ml 5g

pH (25ºC) 6.70

The above samples (1) to (7) were developed and then evaluated for sensitivity, fog, sharpness and discoloration. In this regard, the values of relative sensitivity at a density of 1.0 were obtained by using the relative sensitivity value of the sample (1) as 100 for convenience, the values of fog were obtained in the development times of 3 minutes 30 seconds and also in the accelerated development time of 7 minutes, and the values of sharpness were obtained by determining the CTF (contrast transfer function) (%) at a spatial frequency of 15 cycles/mm, with the higher value of sharpness being the better. In addition, the values of dark discoloration were obtained by leaving each of the developed samples at 80°C and 70% RH for 14 days and evaluating the percentage of density obtained in 14 days with respect to the area having a color density of 2.0 obtained before the test. The results are shown in Table 3. Table 3 Sample Sensitivity Value of 3.5 min. Fog 7 min. Sharpness Dark discoloration Control Present invention

As clearly shown in Table 3, the samples of the present invention prepared by combining cyan couplers and dyes are good photographic materials having high sensitivity, less fogging, high sharpness and good resistance to dark discoloration.

Example 2

Sample (8) having the following composition was prepared in the same manner as in Example 1.

The 1st layer (blue-sensitive silver halide emulsion layer)

Monodisperse silver chlorobromide emulsion containing a spectral sensitizer (Sen-6) (EM-7) 0.27

Gelatin 1.86

Yellow coupler (ExY) 0.82

Solvent (Solv-4) 0.35

Hardener (Hd) 0.02

The second layer (color mixing prevention layer)

Gelatin 0.99

Color mixing preventive agent (Cpd-4) 0.06

Solvents (Solv-3 and Solv-4 in a 0.12

Volume ratio of 1:1)

Hardener (Hd) 0.02

The third layer (green-sensitive silver halide emulsion layer)

Monodisperse silver chlorobromide emulsion containing spectral sensitizers (Sen-7, 3) (EM-8) 0.45

Gelatin 1.24

Magenta coupler (ExM) 0.35

Color Image Stabilizer (Cpd-6) 0.20

Color Image Stabilizer (Cpd-7) 0.03

Color Image Stabilizer (Cpd-8) 0.03

Solvent (Solv-3 and Solv-5 in a volume ratio of 1:2) 0.65

Hardener (Hd) 0.01

The fourth layer (ultraviolet absorption layer)

Gelatin 1.58

Ultraviolet absorber (UV-1/2/3 in a molar ratio of 1:4:4) 0.62

Colour mixing inhibitor (Cpd-4) 0.05

Solvent (Solv-6) 0.34

Dye (Dy-1) 1.8x10⊃min;⊃5; (mol/m²)

Dye (Dy-2) 2.0x10⊃min;⊃5; (mol/m²)

Hardener (Hd) 0.01

The fifth layer (red-sensitive silver halide emulsion layer)

Monodisperse silver chlorobromide emulsion containing spectral stabilizers (Sen-4, 5) (EM-9) 0.20

Gelatin 0.92

Cyan coupler (Table 5) 6.7x10⊃min;⊃4; (mol/m²)

Polymers (Cpd-3) 0.30

Ultraviolet absorber 0.17

(UV-1/3/4 in a molar ratio of 1:3:3)

Solvent (Solv-4) 0.20

Hardener (Hd) 0.01

The sixth layer (ultraviolet absorption layer)

Gelatin 0.53

Ultraviolet absorber (UV-1/2/3 in a molar ratio of 1:4:4)0.21

Solvent (Solv-6) 0.08

Hardener (Hd) 0.01

The seventh layer (protective layer)

Gelatin 1.33

Acrylic denatured copolymer of polyvinyl alcohol (denaturation level 17%) 0.17

Liquid paraffin 0.03

The details of the particles of AgBrCl in the silver halide emulsions used in the above-mentioned samples are shown in Table 4. Table 4 Emulsion Form Average particle diameter (um) Br content (mol%) Coefficient of variation Cube

Coefficient of change = standard deviation/average particle diameter

Samples (8) to (11) were prepared by changing the dyes of the 4th layer and the cyan couplers of the 5th layer in the above-mentioned sample. The compositions are shown in Table 5. Table 5 Sample Dye Cyan coupler (6.7x10⊃min;⊃4; mol/m²) (Amount: mol/m²) Control Present invention

Samples (8) to (11) were exposed to light and treated by the following steps to obtain their evaluation in the same manner as in Example 1. Processing step Temperature (ºC) Time Colour development Bleach-fix Rinse Dry

(A 3-tank countercurrent system of flushing (4) T (1) was used).

The composition of each processing solution is given as follows:

Color development solution

Water 800 ml

Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid 1.5 g

Triethylenediamine-(1,4-diazabicyclo-(2,2,2)-octane) 5.0 g

Sodium chloride 1.4 g

Potassium carbonate 25 g

N-Ethyl-N-(β-methanesulfonamideethyl)-3-methyl-4-aminoaniline sulfate 5.0 g

N,N-Diethylhydroxylamine 4.2 g

Brightening agent (UVITEX CK manufactured by Ciba Geigy Co., Ltd.) 2.0 g

Water rest to 1000 ml

pH value (25ºC) 10.10

Bleach-fixing bath

Water 400ml

Ammonium thiosulfate (70%) 100 ml

Sodium sulphite 18 g

Iron(III) ammonium ethylenediaminetetraacetate 55 g

Disodium ethylenediaminetetraacetate 3g

Aminonium bromide 40 g

Glacial acetic acid 8g

Water rest to 1000 ml

pH (25ºC) 5.5

Rinse bath

Ion exchange water (calcium and magnesium at 3 ppm or less each).

Samples (8) to (11) were developed and evaluated in the same manner as in Example 1, whereby the sensitivity values were obtained when the relative sensitivity of Sample (8) was considered to be 100 and the values of fog formed by the accelerated development were obtained, when the development time was 90 seconds. The results are shown in Table 6. Table 6 Sample Sensitivity Value of 3.5 min. Fog 7 min. Sharpness Dark discoloration Control Present invention

As clearly seen from Table 6, the samples containing the combination of cyan couplers and dyes are good photographic materials which have high sensitivity, low fogging values, high sharpness and good resistance to dark discoloration.

Example 3

To test the stability of the dyes of the present invention in the films, samples (2), (4), (7), (9) and (11) of Examples 1 and 2 were allowed to stand at 35°C and 80% RH for 2 weeks and then evaluated to determine the percentages of the dyes remaining. The results are shown in Table 7. Table 7 Sample Percent of dyes remaining Control Present invention

The results show that the dyes according to the invention have good stability in films.

The present invention can provide silver halide color photographic materials having hydrophilic colloid layers containing novel dyes which are easily decolored by processing and are stable even with the passage of time without exerting any harmful effect on the photographic properties of the photographic emulsions, particularly on sensitivity and fog. In addition, the present invention can provide silver halide color photographic materials including a red-sensitive emulsion layer which has good resistance to dark discoloration, high sharpness, high sensitivity and low fog.

Claims (11)

1. A silver halide color photographic material comprising a support having applied thereon at least one silver halide color photographic emulsion, and containing at least one compound represented by the following general formula (I) and at least one compound represented by the following general formula (II) in at least one hydrophilic colloid layer provided on the support: wherein R₁ and R₂ are each -COOR₅ or -CON represent; R₃ and R₄ each represent hydrogen or an alkyl group; R₅ and R₆ each represent a hydrogen atom, an unsubstituted alkyl group or an aryl group, or R₅ and R₆ together form a 5- or 6-membered ring; Q₁ and Q₂ each represent an aryl group; X₁ and X₂ each represent a divalent bonding group or a bond; Y₁ and Y₂ each represent a sulfonic acid group or a carboxylic acid group; L₁, L₂ and L₃ each represent a methine group; m₁ and m₂ each represent 1 or 2; n represents 0, 1 or 2; P₁ and P₂ each represent 0, 1, 2, 3 or 4; and S₁ and S₂ each represent 1 or 2; and wherein Y₃ represents -NHCO- or -CONH-; R₈ represents an aliphatic group, an aromatic group, a heterocyclic group or an arylamino group which may be substituted; X₃ represents hydrogen, a halogen atom, an alkoxy group or an acylamino group; R₇ represents an alkyl group (containing two or more carbon atoms); and Z represents a hydrogen atom or a group which can be released by coupling with an oxidized color developing agent, wherein the photographic material does not contain a silver halide emulsion layer of the non-prefogged latent image type. 2. The silver halide color photographic material according to claim 1, wherein the compound represented by the formula (I) is used in such an amount that the compound provides an optical density of 0.05 to 3.0. 3. The silver halide color photographic material according to claim 1 or 2, wherein the compound represented by formula (I) is incorporated into at least one of the hydrophilic colloid layers. 4. The silver halide color photographic material according to any one of claims 1 to 3, wherein the amount of the compound represented by formula (II) is 0.1 to 1.0 mol per mol of silver halide in the silver halide photographic emulsion layer containing the compound. 5. The silver halide color photographic material according to any one of claims 1 to 4, wherein the alkyl group represented by R5 or R6 is substituted with a substituent selected from the group consisting of a sulfo group, a carboxyl group, a hydroxyl group, an alkoxy group, a halogen atom, a cyano group, an aliphatic or aromatic sulfonyl group, a nitro group, an unsubstituted amino group or an amino group substituted with an alkyl group, and an aryl group. 6. The silver halide color photographic material according to any one of claims 11 to 4, wherein the aryl group represented by R5 or R6 is an unsubstituted phenyl group or a phenyl group substituted with a substituent selected from the group consisting of a sulfo group, a carboxyl group, a hydroxyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, an unsubstituted amino group or an amino group substituted with an alkyl group and an alkyl group. 7. A silver halide color photographic material according to any one of claims 1 to 6, wherein R₁ and R₂ each represent a sodium salt, a potassium salt, an ammonium salt or a tetraaminonium salt. 8. The silver halide color photographic material according to any one of claims 1 to 7, wherein the aryl group represented by Q₁ or Q₂ is a 2- or 3-valent phenyl or naphthyl group or a phenyl group substituted with a substituent selected from the group consisting of a C₁ to C₄ alkyl group, a C₁ to C₄ alkoxy group, a halogen atom, an aliphatic or aromatic carbamoyl group, an aliphatic or aromatic sulfamoyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, an unsubstituted amino group or an amino group substituted with an alkyl group, an aliphatic or aromatic acylamino group and an aliphatic or aromatic sulfonamido group. 9. A silver halide color photographic material according to any one of claims 1 to 8, wherein X₁ and X₂ are each or a bond, wherein R₇ is hydrogen, a C₁-C₅ alkyl group or a C₁-C₅ (total) substituted alkyl group having a substituent selected from the group consisting of a C₁-C₃ alkoxy group, a sulfo group, a carboxyl group, a cyano group, a hydroxyl group, an unsubstituted amino group or an amino group substituted with an alkyl group, an aliphatic or aromatic sulfonamido group, an aliphatic or aromatic carbonamido group, an aliphatic or aromatic carbamoyl group and an aliphatic or aromatic sulfamoyl group. 10. The silver halide color photographic material according to any one of claims 1 to 9, wherein Y₁ and Y₂ each represent a sulfonic acid group or a carboxylic acid group capable of forming a free acid or a salt. 11. The silver halide color photographic material according to any one of claims 1 to 10, wherein L₁, L₂ and L₃ each represent a methine group or a methine group substituted with a substituent selected from the group consisting of a methyl group, an ethyl group and a phenyl group.